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纸质出版日期:1966-3-20,
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孙桐, 张安秋, 金菊花, 黄素琴, 钱宝钧. 纤维素的高分子化学转化及其变性的研究——ⅩⅤ.纤维素在高铈盐溶液中的氧化动力学和氧化部位[J]. 高分子学报, 1966,8(1):28-40.
SUN Tong, CHANG AN-CHIOU, JIN JYU-HUA, HUANG SU-CHIN, TSIEN PAO-CHUN. STUDIES ON THE CHEMICAL MODIFICATION OF CELLULOSE ⅩⅤ. MECHANISM OF CELLULOSE OXIDATION AND REACTION SITES ON THE CELLULOSE MACROMOLECULAR CHAIN IN THE Ce~(4+)-H_2O-CELLULOSE SYSTEM[J]. Acta Polymerica Sinica, 1966,8(1):28-40.
孙桐, 张安秋, 金菊花, 黄素琴, 钱宝钧. 纤维素的高分子化学转化及其变性的研究——ⅩⅤ.纤维素在高铈盐溶液中的氧化动力学和氧化部位[J]. 高分子学报, 1966,8(1):28-40. DOI:
SUN Tong, CHANG AN-CHIOU, JIN JYU-HUA, HUANG SU-CHIN, TSIEN PAO-CHUN. STUDIES ON THE CHEMICAL MODIFICATION OF CELLULOSE ⅩⅤ. MECHANISM OF CELLULOSE OXIDATION AND REACTION SITES ON THE CELLULOSE MACROMOLECULAR CHAIN IN THE Ce~(4+)-H_2O-CELLULOSE SYSTEM[J]. Acta Polymerica Sinica, 1966,8(1):28-40. DOI:
从高铈盐水溶液分解动力学角度进一步确定了反应体系的光敏性质。 从水解纤维素、纤素二糖、二醛基纤维素、葡萄糖、葡萄糖甲甙等纤维素模型化合物在高铈盐溶液中的氧化动力学
确定了作为含有多种官能团的高聚物纤维素的氧化动力学方程式是: -(d[Ce~(4+)]/dt)=(k_Ⅰ[Ⅰ]_0+k_Ⅱ[Ⅱ]_0+k_Ⅲ[Ⅲ]_0+……)[Ce~(4+)]其中
[Ⅰ]_0、[Ⅱ]_0和[Ⅲ]_0分别为纤维素中第1、2和3官能团的初始浓度。k_Ⅰ、k_Ⅱ和k_Ⅲ分别为它们的反应速率常数。 不同模型化合物中相同官能团速率常数的对比
确定了速率常数的归属。k_Ⅰ、k_Ⅱ分别为巨分子端基环上的潜醛基和 5、6-乙二醇单元的反应速率常数。证明在纤维素巨分子中至少有三个氧化反应部位。 纤维素巨分子经高铈盐氧化时
每个潜醛基或5、6-乙二醇单元各消耗二个高铈离子
最后都转变为醛基。在消耗一个高铈离子时
可以生成中间络合物——巨分子自由基。自由基位于末端基环的第2位和第5位碳原子上。 第三反应部位位于中间基环上
其反应速率常数虽小
但由于含量很多
故其反应速率不容忽视。第三反应部位的精确位置现尚无法肯定。 用高铈引发所得共聚物主链没有明显的裂解,自由基的可能位置表明它可能是接枝一嵌段复合共聚物。
In relation to the graft copolymerization of cellulose using Ce4+as catalyst,the me-chanism of eellulose oxidation and the reaction sites on the cellulose macromolecular chain in Ce4+-H2O-cellulose system were studied.From the experimental data concerning the rate of reduction of Ce4+ to Ce3+ in aqueous solution,the photosensitive character of this system has been confirmed.From the rates of oxidation of eellulose and its related model compounds,such as hydrocellulose,cellobiose,dialdehydeceIlulose,glucose and methylglucoside,as determined in eerie salt solution,the kinetics of cellulose oxidation may be represented bv the fol- lowing equation:where [I]0,[II]0 and [III]0 are the initial concentrations of the functional groups of type I,II and III,and kI,kII and kIII are their reaction rate constants respectively.By determining and comparing the rate constants of the same type but of different cellulose model compounds,it was found that the values of k for the same functional group are approximately equal irrespective of the model compounds to which the particular type of functional group is attached.It was also confirmed that there are at least three oxidation sites on a cellulose macfomolecular chain.The sites of greater and medium reactivity are the aldehyde group and 5
6-glycol unit of the terminal anhydroglucose unit respectively.The least reactive site is the hydroxyl groups attached to the third position of the rest of anhydroglucose rings.Though the value of kIII is very small,nevertheless,the reaction of third position should not be neglected for the number of such hydroxyl groups is great. When cellulose is oxidized by ceric salt,it was found that one mole of terminal aldehyde group or 5,6-glycol unit consumes two moles of eerie salt and was finally con-verted into new aldehyde group.Cellulose free radical formed as an intermediate pro-duct initiates the graft copolymerization.Hence,it may be assumed that the copolymer of cellulose obtained by Ce4+ initiation is possibly a graft-block complex copolymer.
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